Pigment dispersion composition and colored photosensitive resin composition containing the same

Abstract

The present invention relates to a pigment dispersion composition and a colored photosensitive resin composition containing the same. The pigment dispersion composition and the colored photosensitive resin composition containing the same comprise: a first pigment dispersion containing a first red pigment having a maximum absorption wavelength of less than 615 nm; and a second pigment dispersion containing a second red pigment having a maximum absorption wavelength of more than 615 nm. The pigment dispersion composition and the colored photosensitive resin composition containing the same have excellent dispersion stability and high red color purity. When forming a pattern, a cured film having excellent adhesion and sensitivity can be formed. Therefore, the pigment dispersion composition and the colored photosensitive resin composition containing the same can be effectively used in a color filter.

Description

Technical Field

[0001] The present invention relates to a pigment dispersion composition and a colored photosensitive resin composition containing the same. Background Art

[0002] Recently, in the field of liquid crystal displays, color liquid crystal display devices that can display images with vivid colors, light and dark, etc. have gradually attracted attention. As an example, the color liquid crystal display device includes: a thin film transistor array substrate having a thin film transistor (TFT) device, a pixel electrode and an alignment layer; and a liquid crystal layer formed in a gap between the color filter and the thin film transistor array substrate.

[0003] The color liquid crystal display device requires high-speed responsiveness, high contrast (brightness-darkness ratio), wide viewing angle, high color purity and other display performances, which can be controlled by the physical properties of the color filter formed in the liquid crystal display device.

[0004] In view of this, researchers have conducted research on various pigment dispersions or photosensitive resin compositions for color filters. For example, in order to improve the color purity required for liquid crystal display devices, the content of colorants used in pigment dispersions or photosensitive resin compositions has been increased.

[0005] However, if the content of the colorant used in the pigment dispersion or the photosensitive resin composition is increased, the transmittance to unnecessary wavelengths, for example, wavelengths below 430 nm, can be reduced, but there is a problem of reduced adhesion and sensitivity when forming a pattern.

[0006] In addition, research is being conducted on a pigment dispersion and a photosensitive resin composition using CI Pigment Red 291 as a red pigment. However, in this case, although excellent adhesion and sensitivity can be exhibited, unnecessary colors are transmitted at wavelengths below 430nm, thereby causing problems such as a significant decrease in red color purity.

[0007] Therefore, there is a need to develop a pigment dispersion and a photosensitive resin composition that can improve the required adhesion and sensitivity and increase the color purity when forming a pattern.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent document 1: Korean Patent Publication No. 2019-0034820. Summary of the invention

[0011] An object of the present invention is to provide a pigment dispersion composition having high red color purity and capable of forming a cured film having excellent adhesion and sensitivity when patterned, and a colored photosensitive resin composition containing the same.

[0012] Still another object of the present invention is to provide a cured film and a color filter using the pigment dispersion composition or a colored photosensitive resin composition containing the same.

[0013] The present invention provides a pigment dispersion composition, which comprises: a first pigment dispersion comprising a first red pigment and a first binder; and a second pigment dispersion comprising a second red pigment and a second binder, wherein the first red pigment has a maximum absorption wavelength less than 615 nm, and the second red pigment has a maximum absorption wavelength greater than 615 nm.

[0014] Furthermore, the present invention provides a colored photosensitive resin composition, which includes the pigment dispersion composition, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

[0015] Meanwhile, the present invention provides a cured film formed from the above-mentioned colored photosensitive resin composition.

[0016] Furthermore, the present invention provides a color filter prepared from the above-mentioned colored photosensitive resin composition.

[0017] The pigment dispersion composition of the present invention and the colored photosensitive resin composition containing the same can form a cured film having excellent dispersion stability, high red color purity, and excellent adhesion and sensitivity when forming a pattern. Furthermore, the color filter prepared from the above-mentioned pigment dispersion composition and the colored photosensitive resin composition containing the same can present an image with excellent image quality. DETAILED DESCRIPTION

[0018] A pigment dispersion composition according to an example of the present invention comprises: a first pigment dispersion comprising a first red pigment and a first binder; and a second pigment dispersion comprising a second red pigment and a second binder, wherein the first red pigment has a maximum absorption wavelength less than 615 nm, and the second red pigment has a maximum absorption wavelength greater than 615 nm.

[0019] The pigment dispersion composition of the present invention may include a first pigment dispersion having a first red pigment having a maximum absorption wavelength of less than 615 nm, thereby having improved dispersion stability, forming a fine pattern to form a cured film with excellent sensitivity, and the above-mentioned pigment dispersion composition may include a second pigment dispersion having a second red pigment having a maximum absorption wavelength of more than 615 nm, thereby having extremely high red color purity, and can reduce the transmittance to unnecessary wavelengths, for example, wavelengths below 430 nm. Therefore, the pigment dispersion composition including the above-mentioned first pigment dispersion and the second pigment dispersion has excellent dispersion stability, and not only that, but also high red color purity, and can show excellent sensitivity when forming a pattern.

[0020] Specifically, the first pigment dispersion includes a first red pigment and a first binder.

[0021] The maximum absorption wavelength of the first red pigment is less than 615 nm. Specifically, the maximum absorption wavelength of the first red pigment may be less than 613 nm, for example, 560 nm to 613 nm, 570 nm to 612 nm or 590 nm to 612 nm. In this case, the maximum absorption wavelength refers to the wavelength at which maximum absorption occurs when the absorption spectrum is measured. When the maximum absorption wavelength of the first red pigment satisfies the above range, the dispersion stability of the pigment dispersion composition can be improved, and a fine pattern can be formed to form a cured film with excellent sensitivity.

[0022] Based on the CIE 1931 color coordinates (x, y), the x value of the first red pigment can be greater than 0.58 and less than 0.66, greater than 0.60 and less than 0.66, or greater than 0.62 and less than 0.66, and the y value can be greater than 0.31 and less than 0.35, greater than 0.31 and less than 0.337, or greater than 0.31 and less than 0.324.

[0023] In the range satisfying the maximum absorption wavelength, the first red pigment may be one or more of the group consisting of pyrrolopyrrole diketo, perylene, pyrenone, quinacridone, quinacridonequinone, anthraquinone, anthrone, benzimidazolone, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, thioindigo, isoindoline, isoindolinone, pyranthrone and isoanthrone. Specifically, the first red pigment may include pyrrolopyrrole diketo.

[0024] For example, the first red pigment may include CI Pigment Red 254 represented by the following Chemical Formula 1, CI Pigment Red 291 represented by the following Chemical Formula 2, or a combination thereof.

[0025] Chemical formula 1:

[0026]

[0027] Chemical formula 2:

[0028]

[0029] In the first pigment dispersion liquid of the present invention, the first red pigment may have an average particle diameter of 80 nm to 150 nm, 80 nm to 130 nm, or 90 nm to 120 nm.

[0030] The first binder may include a copolymer of a plurality of monomers of the following Chemical Formulas 5 to 9.

[0031] Chemical formula 5:

[0032]

[0033] Chemical formula 6:

[0034]

[0035] Chemical formula 7:

[0036]

[0037] Chemical formula 8:

[0038]

[0039] Chemical formula 9:

[0040]

[0041] The first binder comprises a first acrylic resin obtained by polymerizing a monomer of Chemical Formula 5 (styrene monomer, SM), a monomer of Chemical Formula 6 (benzylmaleimide, BMI), a monomer of Chemical Formula 7 (phenylmaleimide, PMI), a monomer of Chemical Formula 8 ((2-hydroxypropyl) methacrylate, HPMA) and a monomer of Chemical Formula 9 (2-(acryloyloxy)ethyl succinate, HOA-MS). In the developing step, the first binder is an alkali-developable polymer that exhibits developability and plays a basic role in forming a coating film after coating and a structural role in embodying a final pattern.

[0042] When the first pigment dispersion of the present invention includes the first acrylic resin, it is excellent in dispersibility and stability after dispersion, and has a high contrast ratio.

[0043] The first acrylic resin may include repeating units (5) to (9) derived from monomers of Chemical Formulae 5 to 9, respectively, at a molar ratio of 1:1 to 3:1 to 6:1.5 to 5:0.1 to 6, based on the total molar number of repeating units constituting the first acrylic resin. When within the above range, a cured film having excellent adhesion and sensitivity can be formed when patterning.

[0044] The first acrylic resin may be prepared by polymerizing the compounds of Chemical Formulae 5 to 9 according to a common method. For example, the first acrylic resin may be prepared by polymerizing the compounds of Chemical Formulae 5 to 9 at a temperature of 60 to 120° C. under a nitrogen atmosphere.

[0045] The weight average molecular weight (Mw) of the first acrylic resin obtained as above can be 3000 g / mol to 20000 g / mol, specifically, 5000 g / mol to 15000 g / mol or 6000 g / mol to 12000 g / mol. In addition, the acid value of the first acrylic resin can be 80 KOHmg / g to 150 KOHmg / g, specifically, 90 KOHmg / g to 120 KOHmg / g.

[0046] The first pigment dispersion may further include a first dispersant and a first solvent.

[0047] The first acrylic resin is mixed with the first red pigment, the first dispersant, and the first solvent and then sealed, thereby preparing the first pigment dispersion of the present invention.

[0048] Based on the total weight of the first pigment dispersion, the first pigment dispersion contains 15 to 25 weight percent of the first red pigment, and based on 100 parts by weight of the first red pigment, it may contain 1 to 100 parts by weight of the first dispersant, 1 to 100 parts by weight of the first binder, and 100 to 300 parts by weight of the first solvent.

[0049] Next, within the above content range, a raw material mixture of the corresponding raw materials can be ground and mixed using a bead mill, an attriter, a super mill, a homogenizer, a paint shaker, a ball mill, a sand mill or a horizontal mill. For example, the raw material mixture can be ground using beads of 0.5 mm to 1.6 mm for about 4 hours to 14 hours, thereby refining the particles in the raw materials.

[0050] Furthermore, within the above-mentioned content range, the raw material mixture of the corresponding raw materials is ground and mixed for the first time using a bead mill of 0.5 mm to 1.6 mm, thereby homogenizing the giant agglomerated particles in the raw material mixture (first dispersion process), and the raw material mixture ground for the first time is ground for a second time using tiny beads of 0.3 mm to 0.05 mm, thereby refining the particles in the raw material mixture (second dispersion process) (equipment: paint vibrator).

[0051] Furthermore, the dispersed first pigment dispersion may be aged for a predetermined time, for example, 24 hours to 168 hours, to stabilize the dispersion.

[0052] The first dispersant and the first solvent General materials can be used.

[0053] Specific examples of the first dispersant include dispersants of acrylates such as butyl (meth)acrylate and N,N-dimethylaminoethyl (meth)acrylate; resins containing ethylene double bonds such as styrene-acrylic resin, styrene-methacrylic resin, styrene-acrylic-acrylate resin, styrene-maleic acid resin, styrene-acrylic-acrylate resin, styrene-maleic acid resin, methacrylic acid-methacrylate resin, acrylic acid-acrylate resin, isobutylene maleic acid resin, and vinyl ester resin; resin dispersants such as polyurethane, polycarboxylate, unsaturated polyamide, polycarboxylic acid, polysiloxane, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, polyester, modified polyacrylate, phosphate ester, and polycarboxylic acid, and mixtures thereof, but are not limited thereto.

[0054] Commercially available examples of the first dispersant include Disperbyk-110, 111, 180, 161, 163, 165, 166, 167, 2000, 2001, 2163, LPN-21116, LPN-6919, LPN-21538, LPN-21208 (BYK-chemie), LPN-21324, LPN-21208, PB-821, 822, 880, 881 (Ajinomoto fine-techno), and solsperse 24000 (Lubrizol), etc., which can be used alone or in combination of two or more.

[0055] Specific examples of the above-mentioned first solvent include (poly) alkylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; (poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ethers such as diethylene glycol monoethyl ether, diethylene glycol methyl ethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerol, and mixtures thereof, but are not limited thereto.

[0056] As required, the first pigment dispersion may further include a first dispersing aid that helps the dispersant to reduce the dispersion time of the first pigment dispersion and maintains the viscosity of the first pigment dispersion more stably. The first dispersing aid may be a general material. Moreover, based on 100 parts by weight of the first red pigment, the first pigment dispersion may include 1 to 10 parts by weight of the first dispersing aid.

[0057] On the other hand, the second pigment dispersion may include a second red pigment and a second binder.

[0058] The maximum absorption wavelength of the second red pigment is 615 nm or more. Specifically, for example, the maximum absorption wavelength of the second red pigment may be 615 nm to 680 nm, 620 nm to 680 nm, or 620 nm to 670 nm. When the maximum absorption wavelength of the second red pigment satisfies the above range, the inherent red color purity is extremely high, and the transmittance of other wavelengths is low, so that when applied to a color filter, excellent image quality with high color purity can be provided.

[0059] Based on the CIE 1931 color coordinates (x, y), the x value of the above-mentioned second red pigment can be greater than 0.66 and less than 0.695, greater than 0.66 and less than 0.6835, or greater than 0.66 and less than 0.6832, and the y value can be greater than 0.27 and less than 0.31, greater than 0.284 and less than 0.31, or greater than 0.290 and less than 0.31.

[0060] In the range satisfying the above-mentioned maximum absorption wavelength, the above-mentioned second red pigment may be one or more of the group consisting of pyrrolopyrrole dione, perylene, pyrenone, quinacridone, quinacridone quinone, anthraquinone, anthrone, benzimidazolone, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, thioindigo, isoindoline, isoindolinone, pyranthrone and isoanthrone. Specifically, the above-mentioned second red pigment may include one or more of the group consisting of pyrrolopyrrole dione and organic dye pyrene.

[0061] For example, the second red pigment may include CI Pigment Red 264 represented by the following Chemical Formula 3, CI Pigment Red 179 represented by the following Chemical Formula 4, or a combination thereof.

[0062] Chemical formula 3:

[0063]

[0064] Chemical formula 4:

[0065]

[0066] In the second pigment dispersion liquid of the present invention, the second red pigment may have an average particle diameter of 80 nm to 150 nm, 80 nm to 130 nm, or 90 nm to 120 nm.

[0067] The second binder may include a copolymer of a plurality of monomers of the following Chemical Formula 5 to Chemical Formula 11.

[0068] Chemical formula 5:

[0069]

[0070] Chemical formula 6:

[0071]

[0072] Chemical formula 7:

[0073]

[0074] Chemical formula 8:

[0075]

[0076] Chemical formula 9:

[0077]

[0078] Chemical formula 10:

[0079]

[0080] Chemical formula 11:

[0081]

[0082] In the above chemical formula 11, R 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, a hydrocarbon group having 1 to 13 carbon atoms substituted by a hydroxyl group, or an ester group having 1 to 20 carbon atoms, 3 is a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, or an ester group having 1 to 20 carbon atoms, and X is an oxygen atom or =CH 2 .

[0083] Specifically, R 3 is a hydrogen atom or an ester group having 1 to 20 carbon atoms. More specifically, R 3 For R 4 -COO-L-, where R 4 is an alkyl or alkenyl group having 1 to 6 carbon atoms, and L is an alkylene group having 1 to 13 carbon atoms.

[0084] For example, the above Chemical Formula 11 may include 11-phosphonoundecyl acrylate represented by the following Chemical Formula 11-1.

[0085] Chemical formula 11-1:

[0086]

[0087] The second binder may include a second acrylic resin obtained by polymerizing a monomer of Chemical Formula 5 (styrene monomer, SM), a monomer of Chemical Formula 6 (benzylmaleimide, BMI), a monomer of Chemical Formula 7 (phenylmaleimide, PMI), a monomer of Chemical Formula 8 ((2-hydroxypropyl) methacrylate, HPMA), a monomer of Chemical Formula 9 (2-(acryloyloxy)ethyl succinate, HOA-MS), a monomer of Chemical Formula 10 (glycidyl methacrylate, GMA) and a monomer of Chemical Formula 11 (phosphoric acid monomer). In the development step, the second acrylic resin is an alkali-developable polymer that exhibits developability and plays a basic role in forming a coating film after coating and a structural role in embodying the final pattern.

[0088] When the second pigment dispersion of the example of the present invention includes the second acrylic resin, a cured film having excellent adhesion and sensitivity can be formed when patterning.

[0089] The second acrylic resin may include repeating units (5) to (11) derived from monomers of Chemical Formulae 5 to 11, respectively, at a molar ratio of 1:0.5 to 3:0.5 to 5:1 to 6:0.1 to 7:0.1 to 8:0.1 to 10, based on the total molar number of repeating units constituting the second acrylic resin. When within the above range, a cured film having excellent adhesion and sensitivity can be formed when patterning.

[0090] The desired second acrylic resin can be prepared by polymerizing the monomers of Chemical Formulas 5 to 11 according to a common method. For example, the desired second acrylic resin can be prepared by polymerizing the monomers of Chemical Formulas 5 to 11 at a temperature of 60 to 120° C. under a nitrogen atmosphere.

[0091] For example, in a nitrogen atmosphere, the monomers of Chemical Formulas 5 to 9 are subjected to a first polymerization reaction at a temperature of 60 to 120° C. to obtain a copolymer, and then the monomers of Chemical Formulas 10 and 11 are added to the obtained copolymer and a second polymerization reaction is carried out at a temperature of 60 to 120° C. to prepare the required second acrylic resin.

[0092] The weight average molecular weight (Mw) of the second acrylic resin obtained as above may be 3000 g / mol to 20000 g / mol, specifically, 5000 g / mol to 15000 g / mol or 6000 g / mol to 12000 g / mol. Also, the acid value of the second acrylic resin may be 80 KOHmg / g to 150 KOHmg / g, specifically, 100 KOHmg / g to 130 KOHmg / g.

[0093] On the other hand, the second binder contained in the second pigment dispersion may contain the first acrylic resin, or may be a mixture of the first acrylic resin and the second acrylic resin, within a range not impairing the effects of the present invention.

[0094] Likewise, the first binder contained in the first pigment dispersion may contain the second acrylic resin as long as the effect of the present invention is not impaired, or may be a mixture of the first acrylic resin and the second acrylic resin.

[0095] According to an example of the present invention, when the first binder contained in the above-mentioned first pigment dispersion contains the above-mentioned first acrylic resin, and the second binder contained in the above-mentioned second pigment dispersion contains the above-mentioned second acrylic resin, it is more advantageous to form a cured film with adhesion and sensitivity when forming a pattern.

[0096] The second pigment dispersion may further include a second dispersant and a second solvent.

[0097] The second pigment dispersion of the present invention can be prepared by mixing the second acrylic resin with the second red pigment, the second dispersant, and the second solvent and then sealing.

[0098] Based on the total weight of the second dispersion, the second pigment dispersion may include 15 to 25 weight percent of the second red pigment, and based on 100 parts by weight of the second red pigment, may include 1 to 100 parts by weight of the second dispersant, 1 to 100 parts by weight of the second binder, and 100 to 300 parts by weight of the second solvent.

[0099] The second pigment dispersion liquid may be prepared by the same method as the first pigment dispersion liquid.

[0100] As the second dispersant and the second solvent, commonly used materials can be used, and their specific examples are the same as those described above for the first dispersant and the first solvent, respectively. In addition, the first dispersant and the second dispersant can be the same or different. The first solvent and the second solvent can also be the same or different.

[0101] As required, the second pigment dispersion may include a second dispersing aid that helps the dispersant to reduce the dispersion time of the second pigment dispersion and maintains the viscosity of the second pigment dispersion more stably. The second dispersing aid may be a general material. Moreover, based on 100 parts by weight of the second red pigment, the second pigment dispersion may include 1 to 10 parts by weight of the second dispersing aid.

[0102] In the pigment dispersion composition of the example of the present invention, the weight ratio of the first pigment dispersion and the second pigment dispersion may be 1:0.2 to 3. The weight ratio of the first pigment dispersion and the second pigment dispersion may be 1:0.3 to 3, 1:0.4 to 3 or 1:0.4 to 2.5. When the first pigment dispersion and the second pigment dispersion are mixed in the above weight ratio, the dispersion stability can be improved, the red color purity can be further improved, and excellent sensitivity can be presented when a pattern is formed. In this case, if the content of the first pigment dispersion is too much, the red color purity may be reduced. If the content of the second pigment dispersion is too much, the dispersion stability and brightness will be reduced, and the sensitivity may be reduced when a pattern is formed.

[0103] On the other hand, the colored photosensitive resin composition of another embodiment of the present invention may include the above-mentioned pigment dispersion composition, a photopolymerizable compound, a photopolymerization initiator and a solvent, and may also include an alkali-developable binder resin, a surfactant, a silane coupling agent, an antioxidant, a stabilizer, a leveling agent, etc. as needed.

[0104] The colored photosensitive resin composition of the present invention including the above components can be prepared by a general method of uniformly mixing the above components. The types and contents of the above components can also be appropriately selected within the ranges generally used.

[0105] On the other hand, according to another example of the present invention, a cured film formed of the colored photosensitive resin composition may be provided.

[0106] The cured film can be formed by applying the colored photosensitive resin composition of the present invention to a desired thickness on a substrate that has been pretreated as required using a spin coating, slit coating, roll coating, screen printing, or painting method, followed by pre-curing (pre-baking) at a temperature of 70° C. to 100° C. for 1 to 10 minutes and removing the solvent.

[0107] The transmittance of the cured film at 380 nm wavelength (i-line) may be 42% or less, 35% or less, 30% or less, 25% or less, 20% or less, or 18% or less. For example, the transmittance of the cured film at 380 nm may be 5% to 42%, 5% to 35%, or 5% to 20%. When the transmittance of the cured film at 380 nm wavelength is greater than 42%, unnecessary colors may be transmitted, and thus the color purity will be reduced.

[0108] Furthermore, the maximum transmission wavelength of the above-mentioned cured film may be greater than 610nm, 615nm or more, 616nm or more, 620nm or more, or 622nm or more. For example, the maximum wavelength of the maximum transmission wavelength of the above-mentioned cured film may be 610nm to 645nm, 615nm to 640nm, or 616nm to 638nm. The above-mentioned maximum transmission wavelength can be measured and evaluated by using a transmission spectrum to determine a wavelength region in which the transmittance is 85% or more based on a coating thickness of 1.0μm. In the case where the maximum transmission wavelength of the above-mentioned cured film is less than 610nm, the red color purity may be reduced.

[0109] The cured film of the present invention has a high maximum transmission wavelength greater than 610nm and a low transmittance in the i-line of 380nm, thereby not transmitting unnecessary colors and transmitting red to the maximum extent, thereby improving the red color purity. In addition, when forming a pattern, the pattern characteristics with excellent sensitivity can be reflected. In the case of the above sensitivity, when forming a pattern, the fine pattern line width of 50μm can be 80% or more, 85% or more, 90% or more, or 95% or more.

[0110] In particular, according to the example of the present invention, when the second pigment dispersion contains the second binder, the above-mentioned effects can be satisfied, and a cured film having excellent adhesion when patterning is provided, and the sensitivity can be further improved. In the case of the above-mentioned adhesion, when patterning, the conventional cured film has a minimum micron pattern size of 30 μm or more, whereas in the cured film formed from the colored photosensitive resin composition of the present invention, the fine pattern of 30 μm can be 50% or more, 60% or more, or 70% or more.

[0111] On the other hand, according to another example of the present invention, a color filter prepared from the colored photosensitive resin composition may be provided.

[0112] For example, the color filter can be prepared by coating the colored photosensitive resin composition on one side of a substrate and repeatedly performing a series of processes such as exposure, development and thermal curing to form a colored layer. The color filter can be prepared by a commonly used method.

[0113] The color filter prepared from the colored photosensitive resin composition can present an image of excellent quality. Therefore, the color filter can be effectively used in an image display device. For example, the color filter can be used in an image sensor, for example, the image sensor can include a CMOS image sensor.

[0114] As described above, the pigment dispersion composition of the present invention and the colored photosensitive resin composition containing the same have excellent dispersion stability and high red color purity. In addition, when patterned, a cured film having adhesion and sensitivity can be formed, thereby being effectively used in image display devices such as color filters.

[0115] The present invention will be described in more detail below by way of examples. The following examples are merely illustrative of the present invention, and the scope of the present invention is not limited thereto.

[0116] Example

[0117] <Preparation of Binder>

[0118] Preparation Example 1: Preparation of the first binder

[0119] Into a 1.0L round flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen inlet tube, 155 gg of propylene glycol monomethyl ether acetate (PGMEA) as a solvent and 87 g of 1-methoxypropane-2-ol (PGME) as a polymerization initiator were added and stirred. 100 g of benzyl maleimide (BMI), 120 g of phenyl maleimide (PMI), 70 g of styrene monomer (SM), 63 g of (2-hydroxypropyl) methacrylate (HPMA) and 22 g of 2-(acryloyloxy) ethyl succinate (HOA-MS) were added, and the mixture was reacted at a temperature of 80°C for 15 hours to obtain a copolymer having a carboxyl group. The above reaction was performed under a nitrogen atmosphere. Analysis of the prepared copolymer (binder) showed that the solid content was 30.5 weight percent, the acid value was 105 KOHmg / g, and the weight average molecular weight (Mw, GPC result) was 10500 g / mol.

[0120] The prepared copolymer (binder) comprises repeating units derived from styrene monomer, benzylmaleimide, phenylmaleimide, (2-hydroxypropyl) methacrylate and 2-(acryloyloxy) ethyl succinate, respectively, in a molar ratio of 1:1.5:1.7:2.1:0.4.

[0121] Preparation Example 2: Preparation of the Second Binder

[0122] The amounts of benzylmaleimide, phenylmaleimide, styrene monomer, (2-hydroxypropyl) methacrylate and 2-(acryloyloxy) ethyl succinate were changed to 98g, 115g, 66g, 65g and 32g respectively, and the same process as Preparation Example 1 was performed to prepare a copolymer having a carboxyl group. Afterwards, 23g of 11-phosphine undecyl acrylate and 12g of glycidyl methacrylate (GMA) as phosphoric acid monomers were added to the obtained copolymer, and the copolymer (binder) solution was prepared by reacting at a temperature of 80°C for 5 hours under a nitrogen atmosphere. The above reaction was performed under a nitrogen atmosphere. The results of analyzing the prepared copolymer (binder) showed that the solid content was 31.8 weight percent, the acid value was 118KOHmg / g, and the weight average molecular weight (Mw, GPC result) was 9800g / mol.

[0123] The prepared copolymer (binder) comprises repeating units derived from styrene monomer, benzylmaleimide, phenylmaleimide, (2-hydroxypropyl) methacrylate, 2-(acryloyloxy)ethylsuccinate and glycidyl methacrylate, respectively, in a molar ratio of 1:1.3:1.5:1.8:0.3:0.7:0.45.

[0124] <Preparation of Pigment Dispersion>

[0125] Preparation Example A: Preparation of Pigment Dispersion 254

[0126] With 100 parts by weight of CI Pigment Red 254 as a base, 80 parts by weight of 1-methoxypropan-2-ol (PGME) as a solvent, 50 parts by weight of a dispersant (Disperbyk-2001 from BYK), 40 parts by weight of a binder prepared in the above-mentioned Preparation Example 1 and 10 parts by weight of a dispersing aid (Solsperse 22000) were mixed, and then pre-mixed at 650 rpm for 60 minutes to prepare a raw material mixture.

[0127] The prepared raw material mixture was ground for 6 hours using a 0.5 to 1.6 mm bead mill, thereby refining particles in the raw material mixture to prepare a pigment dispersion 254 having an average particle size of 105 nm.

[0128] Preparation Example B: Preparation of Pigment Dispersion 291

[0129] The same procedure as that of Preparation Example A was performed to prepare a pigment dispersion 291 having an average particle diameter of 98 nm, except that CI Pigment Red Pigment 291 was used instead of CI Pigment Red Pigment 254.

[0130] Preparation Example C: Preparation of Pigment Dispersion 179

[0131] The same procedure as that of Preparation Example A was performed to prepare a pigment dispersion 179 having an average particle diameter of 113 nm, except that CI Pigment Red Pigment 179 was used instead of CI Pigment Red Pigment 254.

[0132] Preparation Example D: Preparation of Pigment Dispersion 264a

[0133] The same procedure as that of the above-mentioned Preparation Example A was performed to prepare a pigment dispersion 264a having an average particle diameter of 120 nm, except that the CI Pigment Red Pigment 264 was used instead of the CI Pigment Red Pigment 254.

[0134] Preparation Example E: Preparation of Pigment Dispersion 264b

[0135] The same process as that of Preparation Example A was performed to prepare a pigment dispersion 264b having an average particle size of 103 nm, except that CI Pigment Red Pigment 264 was used instead of CI Pigment Red Pigment 254 and the second binder prepared in Preparation Example 2 was used as the binder.

[0136] Example 1

[0137] <Preparation of Pigment Dispersion Composition>

[0138] The pigment dispersion 254 obtained in Preparation Example A as the first pigment dispersion and the pigment dispersion 179 obtained in Preparation Example C as the second pigment dispersion were mixed at a weight ratio of 70:30 to obtain a pigment dispersion composition.

[0139] <Preparation of Colored Photosensitive Resin Composition>

[0140] Based on the solid content, 5.5 weight percent of a photopolymerizable compound, 1 weight percent of a photopolymerization initiator, 0.35 weight percent of an additive and 48.15 weight percent of a solvent are added to 45 weight percent of a corresponding pigment dispersion composition and a stabilization process is performed at a temperature of 8° C. for more than 3 hours to prepare the desired colored photosensitive resin composition.

[0141] In this case, dipentaerythritol hexaacrylate (DPHA, MI-IN SHOKUSA) was used as the photopolymerizable compound, OXE-02 (IRGACURE) was used as the photopolymerization initiator, DIC F-554 (DICKOREA) was used as the additive, and propylene glycol monomethyl ether acetate (PGMEA) was used as the solvent.

[0142] Example 2

[0143] The same procedures as in Example 1 were performed to prepare a pigment dispersion composition and a colored photosensitive resin composition, except that the pigment dispersion 291 obtained in Preparation Example B was used as the first pigment dispersion.

[0144] Example 3

[0145] The same procedures as in Example 1 were performed to prepare a pigment dispersion composition and a colored photosensitive resin composition, except that the pigment dispersion 264a obtained in Preparation Example D was used as the second pigment dispersion.

[0146] Example 4

[0147] The same procedure as in Example 3 was performed to prepare a pigment dispersion composition and a colored photosensitive resin composition, except that the weight ratio of the first pigment dispersion to the second pigment dispersion was changed to 50:50.

[0148] Example 5

[0149] The pigment dispersion composition and the colored photosensitive resin composition were prepared by the same process as in Example 3 except that the weight ratio of the first pigment dispersion to the second pigment dispersion was changed to 30:70.

[0150] Example 6

[0151] The same procedures as in Example 5 were performed to prepare a pigment dispersion composition and a colored photosensitive resin composition, except that the pigment dispersion 264b obtained in Preparation Example E was used as the second pigment dispersion.

[0152] Example 7

[0153] The same process as in Example 1 was performed to prepare a pigment dispersion composition and a colored photosensitive resin composition, except that the pigment dispersion 291 obtained in Preparation Example B was used as the first pigment dispersion, and the pigment dispersion 264a obtained in Preparation Example D was used as the second pigment dispersion.

[0154] Example 8

[0155] The same procedure as in Example 7 was performed to prepare a pigment dispersion composition and a colored photosensitive resin composition, except that the weight ratio of the first pigment dispersion to the second pigment dispersion was changed to 30:70.

[0156] Example 9

[0157] The same procedures as in Example 8 were performed to prepare a pigment dispersion composition and a colored photosensitive resin composition, except that the pigment dispersion 264b obtained in Preparation Example E was used as the second pigment dispersion.

[0158] Comparative Example 1

[0159] The same procedure as in Example 1 was performed to prepare a colored photosensitive resin composition, except that as the pigment dispersion liquid, the pigment dispersion liquid 254 obtained in Preparation Example A was used alone.

[0160] Comparative Example 2

[0161] The same procedure as in Example 1 was performed to prepare a colored photosensitive resin composition, except that as the pigment dispersion liquid, the pigment dispersion liquid 291 obtained in Preparation Example B was used alone.

[0162] Comparative Example 3

[0163] The same process as in Example 1 was performed to prepare a pigment dispersion composition and a colored photosensitive resin composition, except that the pigment dispersion 254 obtained in Preparation Example A and the pigment dispersion 291 obtained in Preparation Example B were mixed in a weight ratio of 50:50 as the first pigment dispersion.

[0164] <Test example>

[0165] Test Example 1: Maximum Transmission Wavelength

[0166] After the colored photosensitive resin compositions prepared in the above-mentioned examples and comparative examples were respectively coated on a glass substrate by spin coating, they were heat treated at a temperature of 100° C. for 10 minutes and cured to form a coating film (cured film). The transmittance spectrum was measured using Hitachi's u4100. The above-mentioned maximum transmission wavelength measurement was based on the coating film thickness of 1.0 μm and the wavelength region where the transmittance was 85% was evaluated.

[0167] Test Example 2: Transmittance at 380nm wavelength

[0168] In the transmission spectrum used in the above-mentioned Test Example 1, the transmittance at a wavelength of 380 nm was confirmed.

[0169] Test Example 3: Adhesion

[0170] The colored photosensitive resin compositions prepared in the above examples and comparative examples were respectively applied on a glass substrate by spin coating, and then heat treated at 100°C for 10 minutes and cured to form a coating film with a thickness of 1.0 μm. Then, a coating mask was applied to the coating film and irradiated with a mercury lamp at 40 mJ / cm 2 Energy. At room temperature, the exposed coating was developed by spraying with a 0.05 weight percent KOH aqueous solution and then washed with distilled water. The remaining fine pattern (pattern line width: 1-40 μm) on the glass substrate was observed by Keynece's VHX-1000E optical microscope at 200 times to determine the remaining minimum fine pattern size.

[0171] The adhesion of the pattern to the substrate was evaluated as follows based on the circular pattern diameter of 30 μm.

[0172] More than 90%: ◎

[0173] 80% to 90%: ○

[0174] 70% to 80%: △

[0175] 60% to 70%: X

[0176] Less than 60%: XX

[0177] Test Example 4: Sensitivity

[0178] The fine pattern was observed and measured by the same method as the adhesion evaluation of Test Example 3 above.

[0179] The sensitivity was evaluated as follows based on the line width of the pattern formed based on a fine pattern line width of 50 μm.

[0180] More than 96%: ◎

[0181] 90% to 96%: ○

[0182] 85% to 90%: △

[0183] 80% to 85%: X

[0184] Table 1

[0185]

[0186] Table 2

[0187]

[0188] From the experimental results in Table 1 above, it was confirmed that the cured film of the example prepared using the pigment dispersion composition containing both the first pigment dispersion and the second pigment dispersion had a lower transmittance of 42% or less at a wavelength of 380 nm and a maximum transmission wavelength of more than 610 nm, compared with the comparative example.

[0189] Specifically, the cured films of Examples 1 to 9 have a maximum transmission wavelength of 616 nm or more, thereby effectively transmitting red, thereby expressing the maximum inherent color, and have a low transmittance of 16.35% to 40.18% at a wavelength of 380 nm, which is a wavelength other than red, thereby rarely transmitting unnecessary colors, thereby further improving the red color purity.

[0190] On the contrary, the cured films of Comparative Examples 1 and 2 using one pigment dispersion have maximum transmission wavelengths of 610 nm and 605 nm, respectively, and high transmittances of 42.60% and 49.20% at a wavelength of 380 nm, respectively. That is, unnecessary colors are transmitted in large amounts at wavelengths outside the red wavelength range, and thus the red color purity may be reduced.

[0191] Furthermore, the cured film of Comparative Example 3 using two first red pigments having maximum absorption wavelengths less than 615 nm has a maximum transmission wavelength of 607 nm similar to Comparative Examples 1 and 2, and has a high transmittance of 46.70% at 380 nm. In this case, the red color purity may be reduced.

[0192] On the other hand, from the experimental results in Table 2, it was confirmed that even when a pigment dispersion composition including the first pigment dispersion and the second pigment dispersion was used, the adhesion and sensitivity of the cured film changed depending on the type of the binder.

[0193] Specifically, as shown in Examples 6 and 9, when the second binder using a phosphoric acid monomer is used, it is possible to maintain high color purity of red and improve adhesion and sensitivity.

[0194] In particular, comparing Example 5 with Example 6 and Example 8 with Example 9, even when the same first red pigment and second red pigment are used, the adhesion and sensitivity of the cured films of Example 6 and Example 9 using the second adhesive are significantly improved compared to the cured films of Example 5 and Example 8.

[0195] Therefore, the pigment dispersion composition of the present invention can improve the transmittance at the required wavelength and reduce the transmittance at the unnecessary wavelength to improve the red color purity, and also show improved effects in terms of adhesion and sensitivity.

Claims

1. A pigment dispersion composition, characterized in that: Include: A first pigment dispersion comprising a first red pigment and a first binder; and The second pigment dispersion includes a second red pigment and a second binder, The first red pigment has a maximum absorption wavelength less than 615 nm, The second red pigment has a maximum absorption wavelength above 615 nm. The weight ratio of the first pigment dispersion to the second pigment dispersion is 1:0.2 to 3. The first binder includes a first acrylic resin having a copolymer of monomers of the following Chemical Formula 5 to Chemical Formula 9, The second binder includes a second acrylic resin having a copolymer of monomers of the following Chemical Formula 5 to Chemical Formula 11-1 or a copolymer of monomers of the following Chemical Formula 5 to Chemical Formula 9: Chemical formula 5: Chemical formula 6: Chemical formula 7: Chemical formula 8: Chemical formula 9: Chemical formula 10: Chemical formula 11-1: The first red pigment includes CI Pigment Red 254 represented by the following Chemical Formula 1, CI Pigment Red 291 represented by the following Chemical Formula 2, or a combination thereof, The second red pigment includes CI Pigment Red 264 represented by the following Chemical Formula 3, CI Pigment Red 179 represented by the following Chemical Formula 4, or a combination thereof: Chemical formula 1: Chemical formula 2: Chemical formula 3: Chemical formula 4:

2. The pigment dispersion composition according to claim 1, characterized in that: Based on the CIE 1931 color coordinates (x, y), the first red pigment has an x ​​value of greater than 0.58 and less than 0.66 and a y value of greater than 0.31 and less than 0.

35. The second red pigment has an x ​​value of 0.66 to 0.695 and a y value of 0.27 to 0.31 based on CIE 1931 color coordinates (x, y).

3. The pigment dispersion composition according to claim 1, characterized in that: The first acrylic resin comprises repeating units (5) to (9) derived from monomers of Chemical Formulae 5 to 9, respectively, at a molar ratio of 1:1 to 3:1 to 6:1.5 to 5:0.1 to 6, based on the total molar number of repeating units constituting the first acrylic resin. The second acrylic resin comprises repeating units (5) to (11) derived from monomers of Chemical Formulae 5 to 11, respectively, at a molar ratio of 1:0.5 to 3:0.5 to 5:1 to 6:0.1 to 7:0.1 to 8:0.1 to 10, based on the total molar number of repeating units constituting the second acrylic resin.

4. The pigment dispersion composition according to claim 1, characterized in that: The first acrylic resin and the second acrylic resin respectively have a weight average molecular weight (Mw) of 3000 g / mol to 20000 g / mol and an acid value of 80 KOHmg / g to 150 KOHmg / g.

5. The pigment dispersion composition according to claim 1, characterized in that: The first pigment dispersion further comprises a first dispersant and a first solvent. Based on the total weight of the pigment dispersion, the first pigment dispersion comprises 15 to 25 weight percent of the first red pigment, based on 100 parts by weight of the first red pigment, 1 to 100 parts by weight of the first dispersant, 1 to 100 parts by weight of the first binder, and 100 to 300 parts by weight of the first solvent. The first red pigment has an average particle size of 80 nm to 150 nm.

6. The pigment dispersion composition according to claim 1, characterized in that: The second pigment dispersion further comprises a second dispersant and a second solvent. Based on the total weight of the pigment dispersion, the second pigment dispersion comprises 15 to 25 weight percent of the second red pigment, based on 100 parts by weight of the second red pigment, 1 to 100 parts by weight of the second dispersant, 1 to 100 parts by weight of the second binder, and 100 to 300 parts by weight of the second solvent. The second red pigment has an average particle diameter of 80 nm to 150 nm.

7. A colored photosensitive resin composition, characterized in that: The invention comprises the pigment dispersion composition according to claim 1, a photopolymerizable compound, a photopolymerization initiator and a solvent.

8. A cured film, characterized in that: The colored photosensitive resin composition according to claim 7 is formed.

9. The cured film according to claim 8, characterized in that The cured film has a transmittance of 42% or less at a wavelength of 380 nm and a maximum transmission wavelength of more than 610 nm.

10. A color filter, characterized in that: Prepared from the colored photosensitive resin composition according to claim 9.

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